Unsymmetrical alkyne binding to a triruthenium centre: Oxidative-addition of diphenyl ditelluride to the furyne cluster [Ru-3(CO)(7)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-dppm)]

Oxidative-addition of PhTe2Ph to the furyne cluster [Ru-3(CO)(7)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-dppm)] (1) results in the isolation of four complexes; (i) the previously reported 54-electron cluster [Ru-3(CO)(6)(mu(3)-Te)(2)(mu-TePh)(2)(mu-dppm)] (5) which results from elimination of trifuryl phosphine, (ii) the furenyl cluster [Ru-3(CO)(5)(mu-eta(2)-C4H3O){mu-P(C4H3O)(2)}(mu-TePh)(2)(mu-dppm)] (6) which results from carbon-hydrogen bond formation and (iii) two new 50-electron complexes [Ru-3(CO)(5)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-TePh)(2)(kappa (2)-dppm)] (7) and [Ru-3(CO)(4)(mu-H){P(C4H3O)(3)}(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-T ePh)(2)(kappa(2)-dppm)] (8) both containing unsymmetrical furyne ligands. The... (More)

Oxidative-addition of PhTe2Ph to the furyne cluster [Ru-3(CO)(7)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-dppm)] (1) results in the isolation of four complexes; (i) the previously reported 54-electron cluster [Ru-3(CO)(6)(mu(3)-Te)(2)(mu-TePh)(2)(mu-dppm)] (5) which results from elimination of trifuryl phosphine, (ii) the furenyl cluster [Ru-3(CO)(5)(mu-eta(2)-C4H3O){mu-P(C4H3O)(2)}(mu-TePh)(2)(mu-dppm)] (6) which results from carbon-hydrogen bond formation and (iii) two new 50-electron complexes [Ru-3(CO)(5)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-TePh)(2)(kappa (2)-dppm)] (7) and [Ru-3(CO)(4)(mu-H){P(C4H3O)(3)}(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-T ePh)(2)(kappa(2)-dppm)] (8) both containing unsymmetrical furyne ligands. The structures of all the new compounds have been unambiguously established by single crystal X-ray crystallography. Further reactivity studies have provided a clear understanding of the relative sequence of the key oxidative-addition and reductive-elimination processes, showing that 6 is an intermediate in the formation of 7. DFT calculations have been used to shed light on the unsymmetrical binding of the furyne ligand in 7 and also to show that the adopted position of the heteroatom within the furyne ring can vary within complexes of this type. (C) 2010 Elsevier B.V. All rights reserved. (Less)

@article{eff003b5-afe6-46ab-afcd-392ecb6ab6d0,
abstract = {Oxidative-addition of PhTe2Ph to the furyne cluster [Ru-3(CO)(7)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-dppm)] (1) results in the isolation of four complexes; (i) the previously reported 54-electron cluster [Ru-3(CO)(6)(mu(3)-Te)(2)(mu-TePh)(2)(mu-dppm)] (5) which results from elimination of trifuryl phosphine, (ii) the furenyl cluster [Ru-3(CO)(5)(mu-eta(2)-C4H3O){mu-P(C4H3O)(2)}(mu-TePh)(2)(mu-dppm)] (6) which results from carbon-hydrogen bond formation and (iii) two new 50-electron complexes [Ru-3(CO)(5)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-TePh)(2)(kappa (2)-dppm)] (7) and [Ru-3(CO)(4)(mu-H){P(C4H3O)(3)}(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-T ePh)(2)(kappa(2)-dppm)] (8) both containing unsymmetrical furyne ligands. The structures of all the new compounds have been unambiguously established by single crystal X-ray crystallography. Further reactivity studies have provided a clear understanding of the relative sequence of the key oxidative-addition and reductive-elimination processes, showing that 6 is an intermediate in the formation of 7. DFT calculations have been used to shed light on the unsymmetrical binding of the furyne ligand in 7 and also to show that the adopted position of the heteroatom within the furyne ring can vary within complexes of this type. (C) 2010 Elsevier B.V. All rights reserved.},
author = {Ghosh, Shishir and Hogarth, Graeme and Kabir, Shariff E. and Nordlander, Ebbe and Salassa, Luca and Tocher, Derek A.},
issn = {0022-328X},
keyword = {Triruthenium,Carbonyls,Furyne cluster,Carbene,Diphenyl ditelluride,Unsymmetrical alkyne binding,Oxidative-addition,X-ray structures},
language = {eng},
number = {10},
pages = {1982--1989},
publisher = {Elsevier},
series = {Journal of Organometallic Chemistry},
title = {Unsymmetrical alkyne binding to a triruthenium centre: Oxidative-addition of diphenyl ditelluride to the furyne cluster [Ru-3(CO)(7)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-dppm)]},
url = {http://dx.doi.org/10.1016/j.jorganchem.2010.10.045},
volume = {696},
year = {2011},
}